Merocyanine dyes containing a sulfone group



United States Patent MEROCYANINE DYES CONTAINING A SULFONE GROUP LeslieG. S. Brooker and Donald W. Heseltine, Rochester, N. Y., assignors toEastman Kodak Company, Rochester, N. Y., a corporation of New Jersey NoDrawing. Application July 12, 1954, Serial No. 442,930

14 Claims. (Cl. 260-240.4)

This invention relates to merocyanine dyes and methods for making them.More particularly this invention relates to merocyanine dyes containinga sulfone group, methods for making such dyes, and photographicemulsions containing these new dyes.

Accordingly, it is an object of our invention to provide new merocyaninedyes containing a sulfone group. Another object is to provide methodsfor making these merocyanine dyes. Still another object is to providephotographic emulsions sensitized with these new merocyanine dyes.Another object is to provide new intermediates useful in preparing thesemerocyanine dyes and a method for making these new intermediates. Otherobjects will become apparent from a consideration of the followingdescription and examples.

The dyes of our invention can advantageously be represented by thefollowing general formula:

wherein R represents an alkyl group, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, n-amyl, carboxymethyl, B-carboxyethyl,carbomethoxymethyl, carbethoxymethyl, fl-hydroxyethyl, ,B-methoxyethyl,allyl (vinylmethyl), benzyl (phenylmethyl), etc. (an alkyl group of theformula CmH2m+1 wherein m represents a positive integer of from 1 to 4,for example), R1 represents a hydrogen atom or an alkyl group (e. g.methyl, ethyl, propyl, etc.), d represents a positive integer of from 1to 3, (when d is 3, R1 is always a hydrogen atom), 11 represents apositive integer of from 1 to 2, Q represents the non-metallic atomsnecessaryto complete a heterocyclic nucleus containing five atoms in theheterocyclic ring (especially where three of said atoms are carbonatoms, one of said atoms is a sulfur atom, and the last atom is a carbonatom or nitrogen atom), and Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus containing from to 6 atomsin the heterocyclic ring, such as those selected from the groupconsisting of those of the thiazole series (e. g. thiazole,4-methylthiazole, S-methylthiazole, 4-phenylthiazole, 5-phenylthiazole,4,5-dimethylthiazole, 4,5-diphenylthiazole, 4- (Z-thienyl) thiazole,etc.), those of the benzothiazole series (e. g. benzothiazole,4-chlorobenzothiazole, 5- chlorobenzothiazole, 6-chlorobenzothiazole,7-chlorobenzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole,6-methylbenzothiazole, S-bromobenzothiazole, 6-bromobenzothiazole,4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole,S-methoxybenzothiazole, 6-methoxybenzothiazole, S-iodobenzothiazole,6-iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole,tetrahydrobenzothiazole, 5,6-dimethoXybenzothiazole, 5,6dioxymethylenebenzothiazole, 5 hydroxybenzothiazole,6-hydroxybenzothiazole, etc.), those of the naphthothiazole series (e.g. a-naphthothiazole (i. e. [2,11-naphthothiazole), fl-naphthothiazole(i. e.

2,748,114 Patented May 29, 1956 ice [1,21-naphthothiazole) S-methoxy [3naphthothiazole, S-ethoxy-fi-naphthothiazole, 7-methoxy anaphthothiazole, S-methoxy-a-naphthothiazole, etc.), those of thethianaphtheno-7,6,4,5-thiazole series (e. g.4-methoxythianaphtheno-7,6,4,5-thiazole, etc.), those of the oxa- Zoleseries (e. g. 4-methyloxazole, S-methyloxaz ole, 4-phenyl0xazole,4,5-diphenyloxazole, 4-ethyloxazo1e, 4,5-dimethyloxazole,5-phenyloxazole, etc.), those of the benzoxazole series (e. g.benzoxazole, S-chlorobenzoxazole, 5 phenylbenzoxazole, 5methylbenzoxazole, 6- methylbenzoxazole, 5 ,6 dimethylbenzoxazole, 4,6dimethylbenzoxazole, S-methoxybenzoxazole, 6-methoxybenzoxazole,S-ethoxybenzoxazole, 6-chl0robenzoxazole, 5 hydroxybenzoxazole, 6hydroxybenzoxazole, etc.), those of the naphthoxazole series (e. g.a-naphthoxazole, fi-naphthoxazole, etc.), those of the selenazole series(e. g. 4-methylselenazole, 4-phenylselenaz0le, etc.), those of thebenzoselenazole series (e. g. benzoselenazole, S-chlorobenzoselenazole,S-methoxybenzoselenazole, 5- hydroxybenzoselenazole,tetrahydrobenzoselenazole, etc.) those of the naphthoselenazole series(e. g. a-naphthoselenazole, fi-naphthoselenazole, etc.), those of thethiazoline series (e. g. thiazoline, 4-methylthiazoline, etc.), those ofthe Z-quinoline series (e. g. quinoline, 3-methylquinoline,S-methylquinoline, 7-methylquinoline, 8- methylquinoline,6-chloroquino1ine, 8-chloroquinoline, G-methoxyquinoline,6-ethoxyquinoline, 6-hydroxyquinoline, S-hydro-xyquinoline, etc.), thoseof the 4-quino1ine series (e. g. quinoline, 6-methoxyquinoline,7-methylquinoline, 8-methylquinoline, etc.), those of the l-isoquinolineseries (e. g. isoquinoline, 3,4-dihydroisoquinoline, etc.), those of the3-isoquinoline series (e. g. isoquinoline, etc.), those of the3,3-dialkylindolenine series (e. g. 3,3-dimethy1indolenine,3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.), those ofthe Z-pyridine series (e. g. pyridine, 3-methylpyridine,4-methylpyridine, S-methylpyridine, 6-methylpyridine,3,4-dimethylpyridine, 3,5-dimethylpyridine, 3,6-dimethylpyridine,4,5-dimethylpyridine, 4,6-dimethylpyridine, 4-chloropyridine, 5-chloropyridine, 6-chloropyridine, 3-hydroxypyridine, 4- hydroxypyridine,S-hydroxypyridine, 6-hydroxypyridine, 3 phenylpyridine, 4phenylpyridine, 6 -phenylpyridine, etc.), those of the 4-pyridine series(e. g. Z-methylpyridine, 3-methylpyridine, 2-chloropyridine,3-ch1or0pyridine, 2,3- dimethylpyridine, 2,5 dimethylpyridine, 2,6dimethylpyridine, Z-hydroxypyridine, S-hydroxypyridine, etc.), etc.

According to our invention, we provide the new dyes represented byFormula I above wherein d represents 1 by reacting together acyclarnmonium quaternary salt selected from those represented by thefollowing general formula:

iodide, thiocyanate, sulfamate, methylsulfate, ethylsulfate,"

perchlorate, benzenesulfonate, p-toluenesulfonate, etc., with a compoundselected from those represented by the following general formula:

wherein Q has the values given above.

The new dyes of our invention represented by Formula I above wherein drepresents 2 or 3 (R1 represents a hydrogen atom) can be prepared bycondensing a cyclammonium quaternary salt selected from thoserepresented by the following general formula:

wherein R, n, X, and Z each have the values given above, q represents apositive integer of from 1 to 2, R3 represents an acyl group (e. g.acetyl, propionyl, benzoyl, etc.), and R4 represents an aryl group (e.g. phenyl, m-, and p-tolyl), together with a compound selected fromthose represented by Formula III.

The new dyes of our invention represented by Formula I above wherein drepresents 2 and R1 represents an alkyl group can advantageously beprepared by condensing together as compound selected from thoserepresented by the following general formula:

wherein R, R2, X, n, and Z each have the values given above and R1 is analkyl group as defined above, with a compound selected from thoserepresented by Formula III above. The intermediates of Formulas II andIV are well known in the art, while the intermediates of Formula V canbe prepared according to the general method described in U. S. Patent2,315,498, issued April The condensations of the compounds of FormulaIII with those of Formulas II, IV, or V can advantageously beaccelerated by heating the reaction mixture, generally temperaturesvarying from ambient temperature (ca. 20 C.) to the reflux temperatureof the reaction mixture being satisfactory. The condensations can becarried out in the presence of an inert solvent, such as pyridine,nitrobenzene, ethanol, n-propanol, isopropanol, n-butanol, etc.

The condensations of the compounds of Formula III with those of Formulas11, IV, or V can advantageously be carried out in the presence of abasic condensing agent, such as the trialkylamines (e. g. triethylamine,tri-n-propylamine, triisopropylamine, tri-n-butylamine,triisobutylamine, tri-n-amylamine, etc.), N-alkylpiperi dines (e. g.N-methylpiperidine, N-ethylpiperidine, etc.), N,N-dialkylanilines (e. g.N,N-dimethylaniline, diethylaniline, etc.), etc.

The intermediates of Formula III above can also be condensed with ap-dialkylaminobenzaldehyde (e. g. pdimethylaminobenzaldehyde, pdiethylaminobenzaldehyde, etc.) in the presence of a basic condensingagent, e. g. piperidine, to give hemioxonol dyes.

The following examples will serve to illustrate the manner whereby thenew dyes of our invention can be prepared.

EXAMPLE 1 5 [(3 ethyl 2(3H) benzoxazolylidene)ethylidene]-3-methyl-2-phenyl-4-thiaz0lid0ne-1 ,1 -dioxide 0 ll o-N-om =CHOH=OCH-CaHs 3-methyl-2-phenyl-4-thiazolidone-1,1-dioxide (1 mol., 2.25 g.),Z-fi-acetanilidovinyl-B-ethylbenzoxazolium iodide (1 mol., 4.34 g.) andtriethylamine (1 mol.-|-40%, 2.0 ml.) were dissolved in ethyl alcohol(25 ml.) and heated under reflux for thirty minutes. The reactionmixture was then chilled overnight and the crude dye filtered off,

4 washed with methyl alcohol and dried. After two recrystallizationsfrom pyridine and methyl alcohol, the yield of pure dye was 2.60 g.(65%). M. P. 238-239 C. dec.

EXAMPLE 2 5 [(3 ethyl 2(3H) benzothiazolylidene)ethyliaenel-3-methyl-2-phenyl-4-th iazolidone-I ,1 -dioxide EXAMPLE 3 5 [(1ethyl-2(1H) quinolylidene)ethylidene] 3-methyl-Z-phenyl-4-thiazolidone-1 ,1 dioxide3-methyl-2-phenyl-4-thiazolidone-l,l-dioxide (1 mol., 2.25 g.),2-B-acetanilidovinyl-l-ethylquinolinium iodide (1 mol., 4.44 g.) andtriethylamine (1 mol.+40%, 2.0 ml.) were dissolved in ethyl alcohol (35ml.) and heated under reflux for thirty minutes.The reaction mixture waschilled overnight, filtered and the crude dye washed with methylalcohol. The crude product was boiled with two 200 ml. portions ofmethyl alcohol, filtered hot and dried. After two recrystallizationsfrom pyridine and methyl alcohol, the yield of pure dye was 3.30 g.(82%); M. P. 273274 C. dec.

EXAMPLE 4 5 [(1 ethyl 2(1H) naphth0[1,2]thiazolylidene) ethylidene] 3methyl 2 phenyl 4 thiazolidone- 1.1 -dioxide s ll3-methyl-2-phenyl-4-thiazolidone-l,l-dioxide (1 mol., 1.12 g.) andZ-B-acetanilidovinyl-l-ethylnaphtho[1,2] thiazolium-p-toluenesulfonate(1. mol., 2.72 g.) were dissolved in ethyl alcohol (20 ml.) andtriethylamine (2 mols., 1.4 ml.) was added. The reaction mixture washeated under reflux-for thirty minutes and was then chilled overnight,filtered, and the crude dye washed with methyl alcohol and dried. Aftertwo recrystallizations from pyridine the yield of purified dye was 1.35g. (58%) and it had M. P. 285-286 C. dec.

5 EXAMPLE 5 3 -mthyl 2 phenyl 5 [(1,3,3 trimethyl 2(3H)-indolylidene)ethylidene] 4 thiazolidone 1,1 dioxide 5 [(5 chloro 3 ethyl2(3H) benzothiazolylidene) ethylidene] 3 methyl 2 phenyl 4 thiazolidone-1,1-dioxide 3-methyl-2-phenyl-4-thiazolidone-1,1-dioxide (1 mol., 1.12g.), 2-B-acetanilidovinyl-S-chloro-3-ethylbenzothiazolium iodide (1mol., 2.42 g.) and triethylamine (2 mol., 1.4 ml.) were heated underreflux for thirty minutes in ethyl alcohol (20 ml.). The reactionmixture was then chilled overnight, the product filtered ofl, thoroughlywashed with methyl alcohol and dried. The yield of purified dye aftertwo recrystallizations from pyridine and methyl alcohol was 0.78 g.(35%). The pure dye had M. P. 293294 C. dec.

EXAMPLE 7 5 (2 p dimethylaminobenzylidene) 3 methyl 2- phenyl 4thiazolidone 1,1 dioxide 3 methyl 2 phenyl 4 thiazolidone 1,1 dioxide (1mol., 2.25 g.) and p-dimethylaminobenzaldehyde (2 mols., 2.98 g.) weredissolved in ethyl alcohol (35 ml.) and two drops of piperidine wereadded. The reaction mixture was then heated under reflux for two hours,chilled overnight and the crude dye filtered oif, washed with methylalcohol and dried. After two recrystallizations from pyridine and methylalcohol, the yield of purified dye was 2.05 g. (57%), M. P. 213-15" C.dec.

EXAMPLE 8 3 benzyl [(3 ethyl 2(3H) benz0xaz0lylidene)- ethylia'ene] 2phenyl 4 thiazolidone 1,1 dioxide 3 benzyl 2 phenyl 4 thiazolidone 1,1dioxide (1 mol., 1.51 g.), 2 5 acetanilidovinyl 3 ethylbenzoxazoliumiodide (1 mol., 2.17 g.) and triethylamine (2 mols., 1.4 ml.) weredissolved in ethyl alcohol and heated under reflux for thirty minutes.The reaction mixture was chilled and the crude dye thrown out ofsolution by the addition, with stirring, of water ml.). The water wasdecanted and the sticky residue taken up in boiling methyl alcohol (30ml.) and chilled overnight. The crude crystalline product was filtered01f, dried and twice recrystallized from methyl alcohol. The yield ofpurified dye was 0.33 g. (14%); M. P. 234236 C. dec.

EXAMPLE 9 3 benzyl 5 [(3 ethyl 2(3H) benzothiazolylidene)ethylidenel 2phenyl 4 thiazolidone 1,1- dioxide 3 benzyl 2 phenyl 4 thiazolidone 1,1dioxide (1 mol., 1.51 g.), 2 [3 acetanilidovinyl 3 ethylbenzothiazoliumiodide (1 mol. 2.25 g.) and triethylamine (2 mol., 1.4 ml.) weredissolved in ethyl alcohol (20 ml.) and heated under reflux for thirtyminutes. The reaction mixture was then chilled and the crude dye thrownout of solution by the addition of water (100 ml.). The water wasdecanted and the crude dye dissolved in methyl alcohol (50 ml), water(200 ml.) was added and the dye extracted with five 200 ml. portions ofether. The ether was removed by distillation and the residue dissolvedin boiling methyl alcohol (50 ml.) and chilled overnight and the crudedye filtered oil and dried. After two recrystallizations from methylalcohol, the yield of pure dye was 0.80 g. (33%), M. P. 188-190 C. dec.

EXAMPLE 10 3 benzyl 5 [(1 ethyl 2(1H)naphth0[1,2lthiazolylidene)ethylidene] 2 phenyl 4 thiazolidone- ],1dioxide 3 benzyl 2 phenyl 4 thiazolidone 1,1' dioxide (1 mol., 1.51 g.),2 ,8 acetanilidovinyl 1 ethylnaphtho[l,2lthiazolium iodide (1 mol., 2.50g.) and triethylamine (2 mols., 1.4 ml.) were dissolved in ethyl alcohol(30 ml.) and heated under reflux for thirty minutes. The cooled reactionmixture was stirred with water ml.) and the dye extracted with eight 200ml. portions of ether. The ether was removed by distillation and theresidue boiled with methyl alcohol (150 ml.) and chilled overnight. Thecrude dye was then filtered off,

washed with methyl alcohol and dried. After two re-- crystallizationsfrom pyridine and methyl alcohol, theyield of purified dye was 0.80 g.(30%), M. P. 218-220 C. dec.

7 EXAMPLE 11 3 benzyl J 5 1 p dime'thylaminobenzylidene i 2 phenyb 4thiazolidone 1,1 dioxide ll CHa C-N-CHz-CoHa -3 benzyl 2 phenyl 4thiazolidone 1,1 dioxide (1 mol., 1.51 g.), 2 pdimethylaminobenzaldehyde '(2 mols., 1.44 g.) and two drops ofpiperidine were dissolved in ethyl alcohol (201ml) and heated underreflux for one hour. The reaction mixture was chilled overnight,

-:filtered, and'the crude dye washed with methyl alcohol and dried.-After two recrystallizations from pyridine and methyl alcohol, theyield of purified dye was 1.61 g. (75%), M. P. 2132l4 C. dec.

EXAMPLE 12 (3-ethyl-2 (3H) -benz0thiaz0lylidene)ethylizlcne]2-methyl-4(5H)-thiaz0l0/ze-1,1-di0xide2-methyl-4(5H)-thiazolone-1,1-dioxide (2 mols., 2.74 g.),Z-fi-acetanilidovinyl-B-ethylbenzothiazolium iodide (1 mol., 4.50 g.)and triethylamine (1 mol., 1.4 ml.)

were dissolved in ethyl alcohol (15 ml.) and heated under reflux forthirty minutes. The reaction mixture was chilled overnight, filtered,and the crude dye dried. -A chloroform solution of the dye was filteredthrough a /2 inch pad of Norit (decolorizing carbon) to removesymmetrical diethylthiacarbocyanine and the chloroform removed bydistillation. After three recrystallizations from methyl alcohol, theyield of purified dye was 2.21 g. (67%), M/P. l39l40 C.

Arzal.Calcd. for C15H14N2S2O3CH3OH: C, 52.6; H, 5.0. Found: C, 53.2; H,5.4.

EXAMPLE 13 5-[(l-ethyl-Z(IH)-naphth0[1,21thiaz0lylidene)ethylidene]-2-me thyl-4(5H) -thiaz0l0ne-1,Z-dioxide O x a N ll C=GH-CH=C CCH:

stirred with methyl alcohol (75 ml.), chilled, and the crude dyefiltered. off. After two recrystallizations from methyl-alcohol, :theyield of purified dye was 1.45 g.

Anal..Calcd..:"for C19H16N2S2O3.CH3 0H: C, 57.8; H, 4.8. Found: C, 57.8;H. 5.0.

8 .IEXAMPLEI 14 5 I -ethyl2(1H -quinolylidene) ethylidene] -2-methyl- 45 H -th iazolon e-] ,1 -dioxide 2-n1ethyl-4(5H)-thiazolone-1,l-dioxide(1 mol., 1.37 g.), Z-fl-acetanilidovinyl-l-ethylquinolinium iodide (l-m0l., 4.44 g.):and.thiethylamine (1 mol., 1.4 ml.) weredissolvedinethyl alcohol (20 ml.) and heated under reflux for-thirtyminutes. The reaction mixture was chilled, diluted with water ml.) andthe crude dye extracted with four 50ml. portionsof chloroform. The

combined chloroform solutions were then filtered through a /2 inch padof Norit (decolorizing carbon), evaporated 'to dryness and the crude dyedissolved in hot methyl alcohol (50 ml.), filtered, and chilledovernight. The crudedye was then filtered off and dried. After tworecrystallizations from methyl alcohol, the yield of purified dye was1.30 g. (40%), M.P. 109-110 C.

EXAMPLE l5 5-[ (.l -ethyl-2 (1H) -quinolylidene ethylidene]-2-methyl- 4(5H) -thiaz0lone-1 ,1 -dioxide 2-methyl-4(5H)-thiazolone-1,1-dioxide (1mol., 1.37 g.), 4-fi-acetanilidovinyl-l-ethylquinolinium iodide (1 mol.,4.44 g.) and triethylamine were dissolved in ethyl alcohol (20 ml.) andheated under reflux for thirty =minutes.

The reaction mixturewas cooled, diluted with Water (100 ml.) and the dyeextracted with four 50 ml. portionsof chloroform. The combinedchloroform solutions were filtered through a /2 inch pad of Norit(decolorizing carbon) and the Norit Washed with an additional 50 ml. ofchloroform. The chloroform was then distilled off and the residuedissolved in hot methyl alcohol (40 ml.), filtered, and chilled. Thecrude product was then'filtered-off and dried. After tworecrystallizations from methyl alcohol the yield of purified dye was0.81 g. (25%), M. P. l25l27 C.

EXAMPLE l6 2-[ (3-ethyl-2 (3H) -benz0xazolylidene) ethylidene] 3(2H)-'thianaphthenone-1,Z-dioxide 3(2H)-thianaphthenone-l,l-dioxide (1mol., 0.91 g.),

1 2 6-acetanilidovinyl-3-ethylbenzoxazolium iodide (1 mol.,

2.17 g.) and triethylamine (2 mols., 1.4 ml.) were dissolved in ethylalcohol (25 ml.) and heated under reflux for thirty minutes. Thereaction mixture was then chilled and filtered and the crude dyethoroughly washed With methyl alcohol and dried. After tworecrystallizations from pyridine and methyl alcohol, the yield was 1.48g. (84%), M. P. 267268 C. dec.

9 EXAMPLE 17 2-[ s-ezh l-z' (3H) -benzthiaz0lylidene) ethylidene] 3 (2H)thianaphtherzone-LI-di0xide 3(2H)-thianaphthenone-1,1-dioxide (1 mol.,0.91 g.), 2-fl-acetanilidovinyl-3-ethylbenzothiazolium iodide (1 mol.,2.25 g.) and triethylamine (2 mols., 1.4'ml.) were dissolved in ethylalcohol (20 ml.) and heated under reflux for thirty minutes. Thereaction mixture was then chilled, filtered, and the crude dyethoroughly washed with methyl alcohol and dried. After tworecrystallizations from pyridine and methyl alcohol, the yield ofpurified dye was 1.51 g. (83%), M. P. 263264 C. dec. EXAMPLE 18 2-(1-ethyl-2(1H)-quin0lylidene)ethylidene] -3 (2H)- thianaphthenone-Z ,1-dioxide \N CH-CHLC 3(2H)-thianaphthenone-1,1-dioxide (1 mol., 0.91 g.),Z-fl-acetanilidovinyl-l-ethylquinolinium iodide (1 11101., 2.22 g.) andtriethylamine (2 mols., 1.4 ml.) were dissolved in ethyl alcohol (20ml.) and heated under reflux for thirty minutes. The reaction mixturewas then filtered hot and the crude dye washed with methyl alcohol anddried. After two recrystallizations from pyridine and methyl alcohol,the yield of purified dye was 1.60 g. (89% M. P. 286287 C. dec.

EXAMPLE 19 2-[(3-ethyl-2 (3H -benzothiazolylidene) isopropylidene} 3(2H) -thianaphthenone-1,1 -dioxide 3(2H)-thianaphthenone-1,1-dioxide (1mol., 1.82 g.), 2-(2-methylmercaptopropenyl)benzothiazole ethylethosulfate (1 mol., 3.89 g.) and triethylamine (1 mol., 1.4 ml.) weredissolved in ethyl alcohol (25 ml.) and heated under reflux for onehour. The reaction mixture was then filtered hot and the crude dyewashed with methyl alcohol and dried. .After two recrystallizations frompyridine and methyl alcohol, the yield of purified dye was 1.70 g.(44%), M. P. 288289 C. dec.

EXAMPLE 20 2-[(1 -ezhyl-2 1 H) -naphthol[1 ,2]thiaz0lylidene)isopropylidene]-3 (2H -thianaphthenone-1 ,1 dioxide3(2H)-thianaphthenone-1,1-dioxide (1 mol., 1.82 g.),l-ethyl-2-(Z-methylmercaptopropenyl) naphtho[l,2]thiazolium ethosulfate(l mol., 4.34 g.) and triethylamine (1 mol., 1.4 ml.) were dissolved inethyl alcohol (25 ml.) and heated under reflux for one hour. Thereaction mixture Was then filtered hot and the crude dye was thoroughlywashed with methyl alcohol and dried. After two recrystallizations frompyridine and methyl alcohol, the yield of purified dye was 1.60 g.(33%), M. P. 28 l2 C.

EXAMPLE 21 2-[] -ethyl-2 1 H -naphth0[1 ,2]thiazolylidene]-3 (2Hthianaph thenone-l ,1 -dioxide 3(2H)-thianaphthenone-1,l-dioxide (0.91g., 1 mol.) and l-ethyl-2-methylmercaptonaphtho[1,2]thiazoliumptoluenesulfonate (3.23 g., 1 mol. plus 50 percent excess) weredissolved in ethyl alcohol (20 ml.) and triethylamine (1.4 ml., 1 mol.plus percent excess) was added. The reaction mixture was then heatedunder reflux for thirty minutes and chilled overnight. The crude dye wasfiltered off, washed with methyl alcohol, and dried. After tworecrystallizations from pyridine and methyl alcohol, the yield ofpurified dye was 1.18 g. (61 percent). M. P. 303-4 C. dec.

EXAMPLE 22 2-(1-ethyl-2(1H) -quinolylidene)-3 (2H) -thianaph thenone-I,1 -a'ioxide 1 1 My) 1 \S/ 1 ethyl 2 -phenylmercaptoquinolinium ptoluenesulfonate (2.19 g., 1 mol.) and 3(2H)-thianaphthenone-1,1-dioxide (0.91 g., 1 mol.) were dissolved in ethyl alcohol (20 ml.)and triethylamine (1.4 ml., 1 mol. plus 100 percent excess) was added.The reaction mixture was heated under reflux for thirty minutes and thecrude dye was thrown out of solution by the addition of water (100 ml.).The crude dye was then stirred with methyl alcohol until crystalline,chilled overnight, filtered, and dried. After two crystallizations frommethyl alcohol, the yield of pure dye was 1.26 g. (75 percent). M. P.206-7 C.

EXAMPLE 23 5-[4-(3-elhyl-2(3H)-benz0thiaz0lylidene)-2-butenylidene]-3-methyl-2-phenyl--zhiazolidone-l ,1 -dioxide were heated under reflux for thirty minutesin pyridine (20 ml.) The reaction mixture was chilled and filtered,

11 the. solid discarded, and the filtrate. treated with methyl alcohol,100 ml., chilled overnight, and. the crude product filtered 011. Aftertwo recrystallizations from pyridine and methyl alcohol, the yield ofpure dye was 0.98 g. (45 percent). M. P. 250-251 C. dec.

EXAMPLE 24 [4 (1 ethyl 2(1H) naphthofl,2]thiazolylidene)- 2butenylidene] 3 methyl 2'- phenyl 4 thiazolid0ne-1,1-di0xide N-CHa 2anilinobutadienyl 1 ethylnaphtho[1,2]thiazolium iodide (2.42 g., 1mol.), 3-methyl-2-phenyl-4-thiazolidone-l,1-dioxide (2.25 g., 1 mol.plus 100 percent excess), acetic anhydride (1.01 g., 1 mol. plus 100percent excess), and triethylamine 1.4 ml., 1 mol. plus 100 percentexcess) were heated under reflux for thirty minutes in pyridine ml.).The reaction mixture was filtered hot and the solid discarded. Thefiltrate was treated with methyl alcohol (100 ml.) and chilledovernight. The crude dye was filtered off, washed with methyl alcohol,and dried. After two recrystallizations from pyridine and methylalcohol, the yield of purified dye was 0.61 g. percent). M. P. 2812 C.dee.

In Examples 23 and 24 above, the intermediate represented by Formula IVwas formed in situ by employing an intermediate similar to that ofFormula IV, except that R3 represents a hydrogen atom, together with acarboxylic anhydride.

We have also found that un-ionized dyes similar to those described inthe copending applications Serial Nos. 282,696, filed April 16, 1952(now abandoned) and 375,279, filed August 19, 1953, of Leslie G. S.Brooker and Frank L. White, now U. S. Patent 2,739,964, issued March 27,1956, can be prepared by reacting together a dye selected from thoserepresented by Formula I above wherein R1 represents a methyl grouptogether with a cyclarnmonium quaternary salt containing an alkylmercapto or aryl mercapto group in a reactive position. The followingtwo examples describe the preparation of such un-ionized dyes.

EXAMPLE 25 2-[di(3-ethyl-2 (3H) -benz0thiaz0lylidene)isopropylidene]-3(2H) -rhianaphthenone1,1-dioxide 2[(3-ethyl-2(3H)-benzothiazolylidene)isopropylidene]-3(2H)-thianaphthenone-1,l-dioxide (0.88 g., 1 mol.), 3-ethyl-2-ethylmercapto benzothiazolium ethylsulfate (3.49 g., 1 mol. plus300 percent excess), and triethylamine (1.4 ml., 1 mol. plus 300 percentexcess) were heated under reflux in pyridine (15 ml.) for thirtyminutes. The reaction mixture was chilled, filtered, and the crudeproduct washed with methyl alcohol. The yield of crude dye was 1.11 g.(81 percent). After two recrystallizations from pyridine the yield ofpurified dye was 0.68 g. (49 percent). M. P.' 340" C.

12 EXAMPLE 26 Z-[diU'ethyI-Z (1H)-naphth0[1,2]thiazolylidene)isopropylidene1-3 2H -th ianaphthenone-I ,1-di0xide C=CHC=CHC 2 [(l-ethyl 2(1H)naphtho[1,2]thiazolylidene)isopropylidene]-3(2H)-thianaphthenone-1,l-dioxide(0.95 g., 1 mol.), 1 ethyl 2 ethylmercaptonaphtho[1,2]thiazoliumethylsulfate (3.99 g., 1 mol. plus 300 percent excess), andtriethylamine (1.4 ml., 1 mol. plus 300 percent excess were refluxed inpyridine (20 ml.) for thirty minutes. The reaction mixture was cooled,filtered, and the crude dye (1.46 g., percent) was filtered off, washedwith methyl alcohol, and dried. After two recrystallizations frompyridine, the yield of purified dye was 0.73 g. (45 percent). M. P. 340C.

Certain of the intermediates represented by Formula III above are newwhile others have been previously described in the prior art. (SeeTroutman and Long, J. A. C. 8., volume 70, page 3436 et seq.) The methodof Troutman and Long was employed to make these intermediates, both newand old, the method comprising heating a compound represented by theformula:

wherein Q has the values given above, together with aqueous hydrogenperoxide in the presence of acetic acid and acetic anhydride. Thefollowing examples will serve to illustrate this method of preparing theintermediates of Formula III.

EXAMPLE 27 2-methyl-4(5H) -thiaz0lone-1,I-dz'oxide2-methyl-4(5H)-thiazolone (1.85 g.) was dissolved in a mixture of aceticacid ml.) and acetic anhydride (40 ml.) in a 500 ml. three-necked flask,fitted with a condenser and thermometer. 30% hydrogen peroxide (40 ml.)was then added and an ice water bath used to maintain the temperaturebelow 60 C. The mixture was allowed to stand overnight and then thesolvent was removed under reduced pressure and the residue dissolved inbenzene (300 ml.). The benzene solution was dried and the benzene wasdistilled off. The product remained as a colorless viscous oil. Theyield was 6.5 g. (58%).

EXAMPLE 28 2-methyl-4 (5H -thiazalone Thioacetamide (1 mol., 37 g.),chloroacetic acid (1 mol., 47.2 g.) and acetic acid (50 ml.) were mixedand heated under reflux for ten minutes. The reaction mixture was pouredinto water (500 ml.), neutralized with sodium carbonate and extractedwith four 200 ml. portions of benzene. The benzene solutions were thenconcentrated and the residual oil distilled under reduced pressure.Theyield of colorless oil was 40 g. (69%), B. P. 120-122 C./ mm.

EXAMPLE 29 3 (2H) -thianaphthenone-1,1 -dioxide 3 (I\CHE Found:

0 C N-R H O CH-R R I R I/ phenyl methyl Do. ethyl D0. n-pr0py1 Do.n-butyl D0. benzyl 4-chlorophenyl methyl Do. ethyl All of the dyes ofour invention are particularly useful in manufacturing photographic,silver halide emulsions, serving to alter the sensitivity thereof;Sensitizationby means of our new dye is, of course, directed primarilyto the ordinarily employed, gelation-silver-halide, developing outemulsions. The dyes are advantageously incorporated in the washed,finished emulsion and should, of course, be uniformly distributedthroughout the emulsion. In

the preparation of photographic emulsions containing our new dyes, it isonly necessary to disperse the dyes in the emulsions. The methods ofincorporating dyes in emulsion are simple and wellknown to those skilledin the art of emulsion making. It is convenient to add'the dyes fromsolutions in appropriate solvents. The solvent must,

of course, be compatible with the emulsion and substan-.

tially free from any deleterious efiect on the light-sensitivematerials. Methanol has proven satisfactory as a solvent for themajority of our new dyes.

The concentration of our new dyes in the emulsion can of flowableemulsion. The concentration of the dye will .vary according to the typeof light-sensitive material-in the emulsion and according to the effectsdesired. The suitable and most economical concentration for any givenemulsion will be apparent to those skilled in the art upon making theordinary tests and observations customarily used in the art of emulsionmaking.

To prepare a gelatino-silver-halide emulsion sensitized with one of ournew dyes,'the following procedure is satisfactory: A quantity of thedyeis dissolved in methyl alcohol or other suitable solvent and a volumeof this solution (which may be diluted with Water) containing from 5 to100 mgs. of dye is slowly added to about 1000 cc. of agelatino-silver-halide emulsion, with stirring. Stirring is continueduntil the dye is uniformly distributed throughout the emulsion. Withmost of our new dyes,

- 14 10 to 20'mgs. of dye per liter of emulsion suffices to pro duce themaximum sensitizing effect with the ordinary gelatino-silver bromide(including bromiodide) emulsions. With fine-grain emulsions, whichinclude most of the ordinarily employed gelatino-silver-chlorideemulsions, somewhat larger concentrations of dye may be necessary tosecure the optimum sensitizing effect.

The above statements are only illustrative and are not to be understoodas limiting our invention in any sense, as it will be apparent that ournew dyes can be incorporated by other methods in many of thephotographic silver halide emulsions customarily employed in the art.For instance, the dyes can be incorporated by bathing a plate or filmupon which an emulsion has been coated, in the solution of the dye, inan appropriate solvent. Bathing methods, however, are not to bepreferred ordinarily.

Photographic silver halide emulsions which can advantageously besensitized by means of the new dyes of our invention comprise thecustomarily employed gelatinosilver-chloride,gelatino-silver-chlorobromide, gelatinosilver-bromide, andgelatino-silver-bromiodide developing-out emulsions.

Photographic silver halide emulsions, such as those listed above,containing the sensitizing dyes of our invention can also contain suchaddenda as chemical sensitizers, e. g. sulfur sensitizers (e. g. allylthiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), variousgold compounds (e. g. potassium chloroaurate, auric trichloride,

etc.) (see U. S. Patents 2,540,085; 2,597,856 and 2,597,915), variouspalladium compounds, such as palladium chloride (U. S. 2,540,086),potassium chloropalladate (U. S. 2,598,079), etc., or mixtures of suchsensitizers; anti-foggants, such as ammonium chloroplatinate (U. S.2,566,245), ammonium chloroplatinite (U. S. 2,566,263), benzotriazole,nitrobenzimidazole, S-nitroinzdazole, benzidine, mercaptans, etc. (seeMees The Theory of the Photographic Process, Macmillan pub., page 460),or mixtures thereof; hardeners, such as formaldehyde (U. S. 1,763,533),chrome alum (U. S. 1,763,533), glyoxal (U. S. 1,870,354), dibromacrolein(Br. 406,750), etc.; color couplers, such as those described in U. S.Patent 2,423,730, Spence and Carroll U. S. application 771,380, filedAugust 29, 1947 (now U. S. Patent 2,640,776), etc.; or mixtures of suchaddenda. Dispersing agents for color couplers, such as those set forthin U. S. Patents 2,322,027 and 2,304,940, can also be employed in theabove-described emulsions.

What we claim as our invention and desire secured by Letters Patent-ofthe United States is:

1. A merocyanine dye selected from those represented by the followinggeneral formula:

wherein R represents a lower alkyl group, and R represents an aryl groupof the benzene series 3. A merocyanine dyeselected from thoserepresented by the following general formula:

wherein R and R each represents a lower alkyl group and R representsanaryl group of the benzene series.

4. A merocyanine dye selected from those represented by-the followinggeneral formula:

wherein R'represents-a lower alkyl group.

5. A merocyanine dye selected from those represented by the followinggeneral formula:

7. The merocyanine dye having the following formula:

8. The merocyanine dye having the following formula:

( lzHs 9. The merocyanine dye having the following formula:

10. The merocyanine dye having the following for- 2H5 11. A process forpreparing merocyanine dyes comprising condensing a compound selectedfrom those represented by the following two general formulas:

and

wherein R and R1 each represents an alkyl group, R2 represents a memberselected from the group consisting of an alkyl group and an aryl group,R represents an acyl group, R represents an aryl group, X represents anacid radical, q represents a positive integer of from 1 to 2, Zrepresents the non-metallic atoms necessary to complete a heterocyclicnucleus containing from 5 to 6 atoms in the heterocyclic ring, itrepresents 1 when Z represents the non-metallic atoms necessary tocomplete a heterocyclic nucleus containing 5 atoms in the heterocyclicring and n represents 2 when Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus containing 6 atoms in theheterocyclic ring together with a compound selected from thoserepresented by the following general formula:

wherein Q represents the non-metallic atoms necessary to complete aheterocyclic nucleus containing five atoms in the heterocyclic ring,three of said atoms being carbon atoms, one of said atoms being a sulfuratom, and one of said atoms being selected from the group consisting ofa carbon atom and a nitrogen atom 12. A process according to claim 11wherein the condensation is carried out in the presence of a basiccondensing agent.

13. A process according to claim 12 wherein the basic condensing agentis triethylamine.

14. A merocyanine dye selected fromthose represented by the followinggeneral formula:

wherein R represents an alkyl group of the formula CniH2m+1 whereinmrepresents a positive integer of from 1 to 4, R1 represents a memberselected from the ,group consisting of a hydrogen atom and a methylgroup, d represents a positive integer of from 1 to 2 when R1 representsa member selected from the group consisting of a hydrogen atom and amethyl ,group and 0! represents 3 when R1 represents a hydrogen atom, Qrepresents the non-metallic atoms necessary to complete a heterocyclicnucleus containing 5 atoms in the heterocyclic ring, 3 of said atomsbeing carbon atoms, 1 of said atoms being a sulfur atom, and l of saidatoms being selected from the group consisting of a carbon atomand anitrogen atom, Z represents the non-metallic atoms necessary to completea heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclicring selected from the group consisting of those of the thiazole series,those of the benzothiazole series, those of the naphthothiazole series,those of the thianaphtheno-7',6',4,5-thiazole series, those of theoxazole series, those of the benzoxazole series, those of thenaphthoxazole series, those of the selenazole series, those of thebenzoselenazole series, those of the naphthoselenazole series, those ofthe thiazoline series, those of the Z-quinoline series, those of the4-quino1ine series, those of the 1 isoquinoline series, those of the3,3-dialkylindolenine series, those of the Z-pyridine series, and thoseof the 4- pyridine series, and n represents 1 when Z represents thenon-metallic atoms necessary to complete a heterocyclic nucleuscontaining 5 atoms in the heterocyclic ring and n represents 2 when Zrepresents the non-metallic atoms necessary to complete a heterocyclicnucleus containing 6 atoms in the heterocyclic ring.

No references cited.

14. A MEROCYANINE DYE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWINGGENERAL FORMULA: